Compound of biodegradable surfactants for separating impurities in a hydrocarbon

ABSTRACT

Compounds of biodegradable surfactants useful for optimizing the separation of impurities typical of hydrocarbons, and designed to intervene and stabilize the molecular structure of crude oil, with no significant alterations of the crude&#39;s intrinsec composition are disclosed. The biodegradable surfactants compounds coexist with a non-ionic surfactant and an organic mix in emulsion form with the purpose of isolating crude from the pipeline, reduce friction to improve crude flow and to enter the crude macromolecule to modify the hydrocarbon chain to reduce its density and thus its viscosity; including compounds of biodegradable surfactants that comprise sodium hydroxide  1 N, potassium chloride, sulphonic acid, dodecanoic acid, nonylphenol, terpene- 1  and water, preferably hard water.

This application is a claims benefit of Serial No. MX/a/2012/000253,filed 2 Jan. 2012 in Mexico and which application is incorporated hereinby reference. To the extent appropriate, a claim of priority is made tothe above disclosed application.

FIELD OF THE INVENTION

The compound of biodegradable surfactants of the present invention hasbeen produced for optimizing the separation of impurities usually foundin hydrocarbons, and it is designed to intervene and stabilize themolecular structure of crude oil, without significantly altering itsintrinsec composition.

Specifically, when the compound of the invention is injected into thereservoir it eliminates the inorganic components present in the aqueousphase while at the same time it regulates the generation of undesiredcompounds such as organic precipitates which are susceptible to changesin temperature, pressure and loss of volatile components.

The use at surface level of this compound, in addition to eliminatinginorganic salts, dispersing asphaltenes and reducing wax content, addsaromatic compounds to the hydrocarbon chain. Further to the above, itreduces crude friction isolating it from the material through which itflows by displacing the crude adhered to the surface of said material.This principle allows the compound of this invention to be usedindustrially as a cleaner of any surface impregnated with crude, or eventhose contaminated with any other oily substance.

STATE-OF-THE-ART

Environmental impact caused by the use of contaminating chemicalproducts is manifold. Damages are to be found in any area where manconducts production activities causing loss of materials, individualproperties and furthermore, irreversible damages to the environment inwater, land and air. The use of chemical products is, to a great extent,the origin of the imbalance of Nature's cycles which can indirectlyaffect human health, even to the point of causing death.

The use of these products in the oil industry is very frequent, both atsurface level as well as down in the reservoir, and it usually impliesthe generation of hazardous waste. With this situation in mind thesearch for developing chemical products that reduce damages and minimizeany kind of detrimental effect that may harm man or his environment isan ongoing activity.

Within this context several initiatives have been attempted to yield asafe product that causes no damage to the environment nor to man andthat may be injected into oil wells for cleansing purposes whileenhancing physical-chemical properties, and thus stimulating oilproduction.

In the process of searching for such a product several patent documentshave been produced, among them U.S. Pat. No. 5,549,839 which disclosesthe formulation of a non-toxic, biodegradable and completely safe tohuman and animal contact industrial solvent. Said compound comprisesd-limonene (73-74% v/v), an etoxilated nonylphenol (16-17% v/v) andfatty acids, namely tall-oil (9-10% v/v). The fatty acid reported inthis document is made up of oleic and linoleic acids, among othersubstances. According to this document the forementioned product ismixed and applied directly and undiluted to an oil spill or other oilproduct residues such as greases and heavy crudes.

In spite of the advances presented in U.S. Pat. No. 5,549,839 forcleaning oil spills or other oil residues, the reported composition hasno surfactant activity nor does it prevent the precipitation of clays orasphaltenes common in crude oil. Furthermore, the product disclosed insaid patent must be applied undiluted to obtain the desired results,this implying that it must be used in large amounts to achieve thecleansing of hydrocarbons.

Another document that addresses the production of a cleansing compoundcomprising biodegradable components is U.S. Pat. No. 4,511,488. Thispatent claims a cleansing compound based on a terpene like d-limonenefor cleaning heavy crudes, greases and asphalt deposits on hard orflexible layers. Said composition comprises 78 to 96% w/w of a mixtureof limonene/surfactant/water in which the individual quantities in themix are 10-60% w/w of limonene, 10-30% w/w of surfactant and 20-70% w/wof water.

According to said claim the compound would use 2-10 parts of a couplingagent and 2-12 parts of additives to adapt the compound for particularuses. Preferably the compound includes glycols, such as ether glycolslike diethylene glycol, hexene glycol or dipropylene glycol. Preferredadditives are softening agents, sequestering agents or corrosioninhibitors. Considered surfactants are anionic surfactants (especiallyamine salts of the dodecylbenzene sulphonic acid), or non-ionicsurfactants like the alkylphenol condensates with 4-5 mols of ethyleneoxide, particularly the nonylphenol condensate.

Just as in U.S. Pat. No. 5,549,839 the compound claimed in U.S. Pat. No.4,511,488 has no surfactant activity, does not prevent clay orasphaltene precipitation and must be used undiluted. This implies highercosts which become higher when considering that the use of otheradditives is necessary, such as glycol ethers, softening andsequestering agents and corrosion inhibitors.

U.S. Pat. No. 5,336,428 must be included to complement thestate-of-the-art information available. This patent refers to a compoundfor degreasing deep-sea off-shore oil drilling platforms made of a mixthat comprises 5-7% w/w of limonene, 15-21% w/w of a non-ionicsurfactant and 0.2-0.4% w/w of an acrylic copolymer as a densifyingagent. According to said document preferred surfactants arepolyethoxylated nonylphenol and the polymer of metacrylic acid andacrylate. In this case the compound is viscous and substantially clear.In similar fashion to the two previous patents mentioned before thiscompound cannot be used in undiluted form because effectiveness is lost.So being the case, the cost of using this product is high.

Considering all the above it becomes evident that in thestate-of-the-art there is a need for a water-based product,biodegradable, highly efficient, fit to be used on crude oil and itsderivatives for enhancing its physical-chemical properties, thatoptimizes flow within production pipelines both downhole and on thesurface, that reduces and disperses organic precipitates, such as waxesand asphaltenes, breaks water-oil emulsions, minimizes organic salts andhydrogen sulphur contents, cleans oily sands and all kinds of surfaces,and that may even be used to reduce organic waste in the environment orfor cleaning animals and birds that have become impregnated with oilbecause of oil spills.

DETAILED DESCRIPTION OF DRAWINGS

FIG. 1. Percentage of biodegradability of the compound of the presentinvention.

FIG. 2. Results of the toxicity test of the compound of the presentinvention taken at different hours.

FIG. 3. Effects of the compound of the present invention on crudeviscosity.

FIG. 4. Effects of the compound of the present invention on emulsionbreaking and oxidized organic precipitates.

FIG. 5. Effects of the compound of the present invention as an enhancerof oil production.

DETAILED DESCRIPTION OF THE INVENTION

The biodegradable surfactants compound of the present invention is achemical combination of a non-ionic surfactant and an organic mix inemulsion form. The purpose of this compound is to isolate crude from thetubing, reduce friction to improve crude flow and to enter the oilmacromolecule to modify the hydrocarbon chain to reduce its density andthus its viscosity.

The biodegradable surfactants compound reported in the presentapplication has been designed for its application on crude oil so thatupon contact with the crude a weak emulsion is formed allowing for avery close interaction between the two; this interaction leads to theextraction of undesired contaminants; at the end the emulsion breaksthus improving the physico-chemical properties of the crude.

This action of the product within the production system is known aspseudoemulsion. This pseudoemulsion produces at its aqueous base anencapsulation of contaminants present thus facilitating their isolationfrom the reservoir and their removal from the system. Furthermore, theproduct is capable of generating a sliding effect between the rockpores, moisturizing it with the aqueous phase and improving oil relativepermeability. Furthermore, the product will work in light and medium oilreservoirs, and achieved great results with heavy and extra-heavycrudes.

A feature of the biodegradable surfactants compound of the presentinvention is that it comprises sodium hydroxide 1N, potassium chloride,sulphonic acid, dodecanoic acid, nonylphenol, terpene-1 and water,preferably hard water.

The compound comprises 60-80% v/v of a mix that comprises 2.5-5.5% v/vof sodium hydroxide 1N, 2-4% v/v of potassium chloride, 5-15% v/v ofsulphonic acid, 3-6% v/v of dodecanoic acid, 3-8% v/v of nonylphenol of4-10 mols and hard water, and 20-40% v/v terpene.

Specifically, the sodium hydroxide 1N is incorporated into the formulaof the invention to dissolve greasy organic compounds with a highmolecular weight and to inhibit precipitation of asphaltic components.

Potassium chloride is used in the formula of the invention to preventclay swelling. This component is added in low concentrations accordingto the environment in which it will be applied and for its use 7 kilosof potassium chloride are diluted in 150 liters of water.

Sulphonic acid performs as a surfactant in the product, its purposebeing to reduce interfacial tension of the water droplets present in theemulsions that contain crude and to facilitate crude transportation,without altering physico-chemical properties. Its concentration in thecompound of the invention is very variable. When used in the oilindustry it is used at very low concentrations in organic solvents.

Dodecanoic acid is incorporated into the compound of the invention dueto its stability and its linear chain which allow it to partially mixwith oil and its derivatives, and because of its polar character whichwarrants that the combination will mix with water. In this formula itsfunction is to stabilize molecular structure.

Another of the components of the formula of the invention is nonylphenolwhich has a varied function in the formula by allowing for the formationof a soft emulsion to join the organic and inorganic components, itbeing a good moisturizer and because it is a non-ionic surfactant it canclean surfaces that require the extraction of oil inorganic contaminantsand mix them with water. Finally, terpene I is an excellent asphaltenedispersant and reducer of greasy components existing in oil, such aswaxes. Its cyclic structure allows it to perfectly dilute in crude andin small water proportions. Preferably, terpene I is limonene terpene.

In one embodiment of the invention the compound optionally comprises oneor more components selected from the group consisting of 8-14% urea,3-8% sodium tripolyphosphate, 2-6% sodium sulphate, 3-6% liquid Genapol,and 1-4% of a quaternary salt.

The procedure for producing the compound of biodegradable surfactants ofthe present invention is also part of the claimed invention, and itcomprises the following steps:

-   -   a. In a clean and dry mixer add an amount no less than 50% v/v        of hard water measured against the total volume of the compound        of the invention, then add 2.5-5.5% v/v of sodium hydroxide 1N        and 2-4% v/v of potassium chloride.    -   b. Then add 5-15% v/v of sulphonic acid, 3-6% v/v of dodecanoic        acid, 3-8% v/v of nonylphenol of 4-10 mols and proceed to shake        well until the mix is homogeneous.    -   c. Once the solution is homogeneous complete the total volume to        100% v/v with hard water without stopping the shaking action.    -   d. Turn the system off and let stand for 24 hours.    -   e. Once the standstill period is over, take 60-80% v/v of the        solution obtained in step d) and mix it with 20-40% v/v of        terpene until a white homogeneous solution is obtained. The        mixing process should be conducted during 30 minutes for amounts        less than 200 liters.    -   f. Let the product obtained in step e) to stand during at least        6 hours and then apply it following safety procedures suggested        for its use.

Among the multiple applications of this compound the following are worthmentioning: formation cleaning for eliminating particles or deposits ofprecipitates, incrustations and such processes that tend to limit crudeflow in the porous layers near the borehole; the extraction of waxes andother precipitates from crude oil; enhancing physico-chemical propertiesof crude oil, such as viscosity, gravity, water content, etc., andstimulation of oil production. Furthermore, depending on theconcentration used, the compound of the invention is applicable todifferent kinds of crude oil, reservoirs of crude oil with different APIgravities, oil production columns, crude oil pipelines, cleaning of flowstations, of bitumen, greases, oily sands and oil spill sites both onland and off-shore, remediation of oily waste pits, treatment ofdrilling muds, animal and vegetation cleaning.

The amount to be prepared will be estimated according to the projecteduse of the compound, whether at surface level or within the reservoir.Before preparing the formula an assessment of the types of contaminantsand concomitants to be removed should be realized so as to determine thecompatibility and concentrations for mixing the components comprised bythe present invention. The concentration of each component of theformula is established according to the acid-basic character that isdesired for the reaction to obtain the desired effect on the crude oil.

EXAMPLES Example 1 Biodegradability Test

The compound of biodegradable surfactants of the present invention wassubject to different biodegradability tests at the EnvironmentalEngineering Laboratory of the University of Zulia with the purpose ofconfirming if it could be used safely without causing harm to theenvironment and furthermore, to see that said compound will be degradedwhen said compound is used as a degreaser or for stimulation ofunreactive wells. Results shown in FIG. 1 show that the compound of theinvention is 40.05% biodegradable after 28 days.

Additionally, Table 1 shows the results of analyses conducted followingthe method described in “Standard Methods for the Examination of Waterand Wastewater”, 1999, 20th edition”, specifically by application ofmethod 5210-B for determining the Biochemical Demand for Oxygen (mg/L)and method 5220-D for establishing the Chemical Demand for Oxygen(mg/L).

TABLE 1 Results of analyses DBO₅, mg/L 30000 DBO₁₀, mg/L 45000 DBO₁₅,mg/L 65000 DBO₂₀, mg/L 85000 DBO₂₈, mg/L 95000 DBO₂₅, mg/L 100000 DQO,mg/L 249680 Rate DBO₅, mg/L 0.1201 Rate DBO₁₀, mg/L 0.1802 Rate DBO₁₅,mg/L 0.2603 Rate DBO₂₀, mg/L 0.3404 Rate DBO₂₅, mg/L 0.3804 Rate DBO₂₈,mg/L 0.4005

Discussion of the results: the information reported in Table 1 clearlyindicates that the compound of the present invention is biodegradablesince the amount of matter susceptible to oxidation by biologicalsources is high as evidenced by the fact that after five days ofreaction the DBO₅ was 30.000 mg/L and after 28 it increased to 100.000mg/L.

Example 2 Toxicity Testing

A number of tests were conducted to establish the degree of toxicity ofthe compound of the present invention by determining its effect on fishin the Lake Maracaibo basin.

The method used for the toxicity test is the one described in “StandardMethods for the Examination of Water and Wastewater”, 1999, 20thedition. Basically the test consisted in running a toxicity bioassay todetermine the lethal concentration of the compound of the presentinvention on the selected bioindicator. The calculated value is called“Mean Lethal Concentration (LC₅₀) and it corresponds to theconcentration that causes death of 50% of the experimental sample aftera certain time. Tables 2 through 5 showing the results of these testsare hereon included:

TABLE 2 Concentration % Control 10 25 50 75 100 pH 7.38 7.78 7.78 7.888.18 8.68 Dissolved oxygen ppm 4.06 5.06 5.09 4.98 4.60 4.58 Salinity(mg/L Cl*) 2000 2000 2000 2000 2000 2000 Observations at the Fish arerestless. They swim normally both horizontally as well as beginning oftesting vertically. They permanently reach to the surface.

TABLE 3 Number of survivors 10 10 10 10 9 9 (%) of Survivors 100 100 100100 90 90 pH 7.86 8.07 7.98 8.01 8.03 7.89 Dissolved oxygen ppm 4.324.94 4.25 4.23 4.75 4.37 Observations during first Dead fish were foundat concentrations 75% & 100%; 1 and 1 24 hours of testing. respectively.The rest of the fish in all concentrations swim normally.

TABLE 4 Number of survivors 100 91 90 90 99 99 (%) of Survivors 100 9090 90 90 90 pH 7.96 8.03 8.12 8.14 8.15 7.95 Dissolved oxygen ppm 4.434.88 4.96 5.02 4.89 4.74 Observations after 48 Again dead fish werefound at concentrations 10%, 25% & 50%; hours of testing. 1, 1 and 1respectively. The rest of the fish in all concentrations swim normally.

TABLE 5 Number of survivors 100 90 90 90 99 99 (%) of Survivors 100 9090 90 90 90 pH 7.96 8.03 8.12 8.14 8.15 7.95 Dissolved oxygen ppm 4.434.88 4.96 5.02 4.89 4.74 Observations after 96 Again dead fish werefound at concentrations 25%, 50%, 75% & hours of testing. 100%; 1, 1, 1,1 respectively and 1 in the control group. The rest of the fish in allconcentrations swim normally.

Likewise, FIG. 2 compiles the results of the toxicity tests conducted onthe compound of the present invention. Conditions for these tests were:

Time intervals 24 h 48 h 96 h LC 50% — — —Concentrations expressed as: %, mg/L; Others: % v/vSpecies used in tests: Revistes

Temperature: 23.5±1.4° C.

Dillution water (characteristics): tap water dechlorinated with chloridesalts to 2000 mg/L.

The procedure for sample preparation (recommended by the VenezuelanInstitute of Crude Oil Technology—INTEVEP, in Spanish) comprises thefollowing steps:

-   -   1. Compound added at the highest concentration required by the        producer (10% v/v),    -   2. Mix well in a blender during 5 minutes,    -   3. Let the solution stand for 14 hours,    -   4. Once the oily, aqueous and sediment layers were separated the        liquid (aqueous) part was taken aside to prepare the bioassay,    -   5. To conduct the toxicity test the following concentrations        were taken from the liquid obtained: 100%, 75%, 50% and 10% of        the diluted fluid.

The method used for the toxicity test was the one described in “StandardMethods for the Examination of Water and Wastewater”, 20th edition,1999, identified as Method number 8010.

Discussion of results: it was not possible to determine LC50 in the testbecause the product did not produce a mortality of 50%.

The results of the toxicity assays show that the product did not producea toxic lethal effect on the live species used (Levistes). It is worthpointing out that during the test a survival level of between 80% and100% was obtained in all concentrations until the end of testing. Thisleads to the conclusion that the compound of the present invention is anon-toxic product and represents a low environmental risk when used atthe concentration that should be used for application according to therequesting party, i.e. 10%.

Example 3 Reduction of Oils and Greases

The compound of the present invention also has an agglutinant effect. Todetermine the degree of this effect an assay was run with the purpose ofdetermining the agglutinant properties that allow cleaning and recoveryof crude oil spills in Lake Maracaibo caused by leaks in the productionsystems. This assay also allowed the determination of the amount ofcrude extracted from the waters when the compounds of the presentinvention come in contact with water.

For this test oil spills were simulated in four (4) experimental units.For the assays 800 mL of water were used to which 4 mL of the compoundof the invention were added at different doses (1, 5 and 10%), and anexperimental unit to which no product was added was used as control.Finally, after ten (10) minutes and after two (2) hours the amount ofcrude in water was measured in each of the experimental units.

Analyses were conducted according to “Standard Methods for theExamination of Water and Wastewater”. 20th Edition, 1999. The methodspecifically followed the parameters for Oils and Greases (mg/L) No.5520-C. Results of the analyses conducted in the laboratory are shown inTables 6 and 7.

TABLE 6 RESULTS OF THE ANALYSES Samples Oils and Greases 10 minutesafter applying product (mg/L) Unit 1: Water with crude; no productapplied 2.81 Unit 2: Water with crude; product applied at 1.0% 0.85 Unit3: Water with crude; product applied at 5.0% 0.72 Unit 4: Water withcrude; product applied at 10.0% 0.58

TABLE 7 RESULTS OF THE ANALYSES Samples Oils and Greases 2 hours afterapplying product (mg/L) Unit 1: Water with crude; no product applied8.63 Unit 2: Water with crude; product applied at 1.0% 0.76 Unit 3:Water with crude; product applied at 5.0% 0.46 Unit 4: Water with crude;product applied at 10.0% 0.37

Discussion of results: results in Table 6 show that application of thecompound of the present invention drastically reduces the concentrationof oils and greases a few instants after adding the product at thedifferent concentrations. Table 7 shows that after two hours in theexperimental unit in which the product was not applied oils and greaseshave dissolved in a greater amount of water whereas in the units wherethe claimed compound was added no dispersion was observed and on thecontrary, concentrations were lower than those seen 10 minutes after theaddition of the product.

Example 4 Tests Regarding the Enhancement Effect on the Physico-ChemicalProperties of the Crude

A SARA study (Saturates, Aromatics, Resins and Asphaltenes) wasconducted to observe the effect of the claimed compound on a medium typecrude from Eastern Zulia state. The study was done at the Institute ofPetroleum Research of the University of Zulia (INPELUZ, acronym inSpanish). Table 8 reports water, sediments, and emulsion content of asample taken from a canal that runs behind the tank station; nonon-ionic surfactant was applied. Table 9 summarizes results of the SARAassessment of the original sample to identify its initial chemicalproperties.

TABLE 8 RESULTS OF ANALYSIS OF THE ORIGINAL SAMPLE CON- SEDIMENTS WATERTAINER (% v/v) (% v/v) EMULSION SAMPLE ID (GALLON) ASTMD 96 ASTM D96 (%v/v) PDVSA- 1 1.00 16.00 12.00 Bachaquero Strong Tank station

TABLE 9 SARA ANALYSIS OF THE ORIGINAL SAMPLE ASPHAL- SATURATES AROMATICSRESINS TENES SAMPLE ID (% w/w) (% w/w) (% w/w) (% w/w) PDVSA- 40.0324.87 28.11 6.98 Bachaquero Tank station

Table 10 reports water, sediments, and emulsion content of a sampletaken from a canal that runs behind the tank station after applying thecompound of non-ionic surfactant of the present invention, and Table 11summarizes results of the SARA assessment of the crude mix with 5% ofthe claimed compound added to determine the chemical effects on thecrude oil.

TABLE 10 RESULTS OF ANALYSIS OF THE TREATED SAMPLE CON- SEDIMENTS WATERTAINER (% v/v) (% v/v) EMULSION SAMPLE ID (GALLON) ASTMD 96 ASTM D96 (%v/v) PDVSA- 1 3.00 16.00 0.00 Bachaquero Tank station

TABLE 11 SARA ANALYSIS OF THE TREATED SAMPLE ASPHAL- SATURATES AROMATICSRESINS TENES SAMPLE ID (% w/w) (% w/w) (% w/w) (% w/w) PDVSA- 40.3632.04 22.04 4.90 Bachaquero Tank station

Discussion of results: data in Tables 8-11 leads to the conclusion thatthe compound of the present invention completely breaks the emulsion.When the compound of the present invention is added the solids in theemulsion separate, as is clearly shown by the increase in sedimentcontent.

Furthermore, results of the SARA chemical analyses (before and aftertreatment) show that by adding 5% of the claimed compoundphysico-chemical properties of the crude are enhanced on account of asubstantial increase in aromatics, a fact that prevents precipitation oforganic solids. It is evident that the application of this compound canbreak emulsions and separate organic and inorganic solids from the flow.

Example 5 Testing to Verify Enhancement of Crude Oil Fluidity Inside aPipeline

The multiple tests run with the compound of the present inventionevidence the double effect it has on crude, both downhole and at surfacelevel, as said compound performs as a friction reducer by encapsulatingcrude and thus preventing its direct contact with the production line,and as a viscosity reducer by enhancing the intrinsec properties ofcrude. Results of said tests are shown below:

TABLE 12 RESULTS OF SAMPLE ANALYSES UNTREATED SAMPLE Kinematic Viscosity@ 100° F. (CST) 7997.99 Kinematic Viscosity @ 180° F. (CST) 517.87 APIgravity 10.8 Asphaltene content (% w/w) 10.32 Wax content (% w/w) 5.61TREATED SAMPLE Kinematic Viscosity @ 100° F. (CST) 1265.68 KinematicViscosity @ 180° F. (CST) 287.24 API gravity 12.80 Asphaltene content (%w/w) 6.32 Wax content (% w/w) 3.68

A similar test was run on a sample taken from a well in the Boscan fieldin the state of Zulia. The purpose was to observe the effect thebiodegradable compound of the present invention had on the crude. Table13 and FIG. 3 show the decrease in viscosity at different temperatures.

TABLE 13 RESULTS OF SAMPLE ANALYSES KINEMATIC VISCOSITY (CST) ASTM D-445SAMPLE COMPOSITION 80° F. 120° F. 180° F. Original crude BN-766 21720.143709.81 517.87 Crude + 5% of product 3988.87 1361.53 287.24

Discussion of results: data in the referred table and figure lead to theassertion that the claimed compound increases the value of API gravityas evidenced by the increase from 10.8° to 12.8° API after adding thecompound in a concentration of 5% v/v, equivalent to 51571.20 ppm.Furthermore, viscosity was lowered in a high percentage going from21720.14 cps to 3988.87 cps after adding the compound in a concentrationof 5% v/v. The test was conducted at 80° F.°. Furthermore, the compoundmixed very well with the crude.

Example 6 Testing to Verify Reduction and Dispersion of OrganicPrecipitates Such as Waxes and Asphaltenes

For these tests a number of analyses were conducted in wells in theBachaquero field, Zulia, to determine the effect of the compound onorganic precipitates.

TABLE 14 ANALYSES OF UNTREATED SAMPLES SAMPLE ID WAXES (% w/w)ASPHALTENES (% w/w) B-2342 (22-07-03) 11.45 4.32 B-2360 (22-07-03) 6.572.94 B-2364 (22-07-03) 10.36 4.65 B-2397 (22-07-03) 5.31 5.23 B-2401(23-07-03) 8.59 6.32

TABLE 15 ANALYSES OF TREATED SAMPLES SAMPLE ID WAXES (% w/w) ASPHALTENES(% w/w) B-2342 (22-07-03) 6.23 3.54 B-2360 (22-07-03) 3.96 2.66 B-2364(22-07-03) 5.78 2.13 B-2397 (22-07-03) 3.24 3.99 B-2401 (23-07-03) 5.693.31

The following work was done by the company Biostar de Venezuela todetermine the effect of the product on light oil from the center of LakeMaracaibo with the purpose in mind to use the product in the reservoirto stimulate production directly in wells. Results of these tests areshown in the following tables:

TABLE 16 ANALYSIS OF UNTREATED SAMPLE Water EMULSION ASPHAL- (% w/w)STANDARD TENES WAXES WELL ASTM D-4007 (% v/v) (% w/w) (% w/w) CLA-001366.00 80.00 Strong 3.47 12.56

TABLE 17 ANALYSIS OF THE SAMPLE ADDING 20% OF THE COMPOUND OF THEINVENTION Water EMULSION ASPHAL- (% w/w) STANDARD TENES WAXES WELL ASTMD-4007 (% v/v) (% w/w) (% w/w) CLA-0013 66.00 0.00 3.36 4.64

Discussion of results: the tested sample contains a high concentrationof wax as can be seen in Table 16. The high concentration of waxstrengthens the emulsion and reduces the effectiveness of conventionaldemulsifiers. By adding the compound of the present invention the amountof wax decreased by 37% forcing emulsion break.

Example 7 Testing to Verify the Effect of the Compound of the PresentInvention in Breaking of Water-Oil Emulsions

Following are the results of treating a crude sample from the Cumarebofield in northwestern Venezuela. The Cu-144 crude sample had an APIgravity of 46.0°. The test was run to determine effects in reducing theemulsion present in the sample.

TABLE 18 ANALYSIS OF UNTREATED SAMPLE SEDIMENTS WATER (% v/v) (% v/v)EMULSION POR SAMPLE ID ASTM D-96 ASTM D-96 (% v/v) Cu-144(12-11-03) 0.0022.00 35.00 Strong

TABLE 19 ANALYSIS OF TREATED SAMPLE SEDIMENTS WATER (% v/v) (% v/v)EMULSION POR SAMPLE ID ASTM D-96 ASTM D-96 (% v/v) Cu-144(12-11-03) 0.0022.00 0.00

Discussion of results: the sample was subject to an emulsion analysis bycentrifugation using 3% of the product. A quick reaction on the crudewas observed and after centrifugation 100% of the emulsion had beenbroken.

A similar result was observed in the crude samples from Bachaquero,eastern Zulia. In that case the tests were run on samples of heavy andextra-heavy crudes. Results were excellent as shown in the followingtables:

TABLE 20 ANALYSIS OF UNTREATED SAMPLE SEDIMENTS WATER (% v/v) (% v/v)EMULSION POR SAMPLE ID ASTM D-96 ASTM D-96 (% v/v) B-2342 (22-07-03)0.00 18.00 24.00 Débil B-2360 (22-07-03) 0.00 0.40  0.80 Fuerte B-2364(22-07-03) 0.00 38.00 76.00 Fuerte B-2397 (22-07-03) 0.00 48.00 50.00Fuerte B-2401 (23-07-03) 0.00 96.00 12.00 Fuerte

TABLE 21 ANALYSIS OF TREATED SAMPLE SEDIMENTS WATER (% v/v) (% v/v)EMULSION POR SAMPLE ID ASTM D-96 ASTM D-96 (% v/v) B-2342 (22-07-03)0.00 18.00 4.00 Débil B-2360 (22-07-03) 0.00 0.40 2.80 Fuerte B-2364(22-07-03) 0.00 38.00 6.00 Débil B-2397 (22-07-03) 0.00 48.00 0.00Fuerte B-2401 (23-07-03) 0.00 96.00 2.00 Fuerte

Example 8 Tests for Assessing the Effects of the Compound of the PresentInvention in Reducing Organic Pollution Such as in Hydrocarbon WastePits

For this test, the physico-chemical characteristics of the samples wereanalyzed first and then it was decided to mix together samples from 8different pits. The mix was divided into 5 parts and the product wasapplied at five different concentrations (3, 5, 10, 15 and 20%) todetermine the effect on the pit sample and establish the possibility ofusing only one specific concentration. Results were that 3 of the 5samples showed an effectiveness of 90-100% and the other 2 of 40%. Ofthe 3 samples with a 90-100% effectiveness only one was taken as areference.

Next, pursuing the objectives set, it was decided to run completeanalyses at the INPELUZ Maracaibo laboratories to establish the puritydegree of the recoverable oil and thus discard any doubt on the possibleconsequences of incorporating the product to the pipeline carrying cleanoil. The procedure developed by the INPELUZ Maracaibo laboratoriesfollows bellow:

-   -   Take a two-liter sample from each pit (8 pits)    -   Manually shake the samples to form a “compound sample”.    -   In a 120 mL bottle add 90 mL of the mix+10 mL of the compound of        biodegradable surfactants of the present invention.    -   Shake during 10 minutes and let stand for 3 hours.    -   Measure the water and sediment content and the interphase, and        record the contents of the different phases.    -   Add 5 drops of a universal emulsion breaker and record the data        corresponding to the different phases.

Following are the results obtained in the test:

Results:

A). With the Composition Reported in this Application:

-   -   Water content: 15.30%    -   Solids: 0.70%    -   Oxidized organic precipitates: 10.0%    -   Crude content: 74%

B). With the Universal Breaker:

-   -   Water content: 25.30%    -   Solids: 0.70%    -   Oxidized organic precipitates: 10.0%    -   Crude content: 64%

A shown by the above results the difference is that water content is 10%greater with the Universal breaker and the crude content is 10% greaterwithout the Universal breaker. FIG. 4 shows pipettes after having addedthe compound of the present invention and its contents shaken. Thebreaking of the emulsion and the oxidized organic precipitates areclearly observed as well as the sediments in the bottom of the pipette.

To conclude, the recommendation is that in view of the results obtainedand its compatibility with the chemical demulsifiers this crude can beinjected in a pipeline leading to a point where it will be mixed withanother crude.

Another case to highlight is the testing conducted on samples from crudeoil pits in Maturin, Eastern Venezuela, by the company Biostar, wherethe compound of the present invention recovered organic as well asinorganic sediments. Recovered organic sediments are reinjected into thecrude production line whereas the inorganic sediments and sand may bereturned to the environment with no harm of any kind to Nature or man.

TABLE 22 ANALYSIS OF UNTREATED SAMPLE Inorganic Organic Water Emulsionsediments Sediments (% w/w) Standard Well (% v/v) (% v/v) ASTM D-4007 (%v/v) OREO-5 pit, 0.40 0.45 13.00 10.00 Strong MATURIN

TABLE 23 ANALYSIS OF THE SAMPLE WITH 2.5% OF THE COMPOUND OF THE PRESENTINVENTION Inorganic Organic Water Emulsion sediments Sediments (% w/w)Standard Well (% v/v) (% v/v) ASTM D-4007 (% v/v) OREO-5 pit, 0.00 0.2513.50 5.00 Weak MATURIN

It is important to mention the use of the compound of the presentinvention by the company BiPetrol as a matrix non-reactive stimulator inwell Samaria-824 in Villahermosa, Mexico. Before injecting the claimedcompound the well produced 27 barrels of crude oil per day with a watercut of 24.00% v/v. The injection aimed at undoing the harm present andpromote the necessary conditions to increase production.

FIG. 5 shows that after treating the well, production increased to morethan 140 barrels per day with a water cut of 7.00% v/v, evidencing theeffects of the compound when used within the reservoir.

1-5. (canceled)
 6. The process of using a compound of biodegradablesurfactants, comprising sodium hydroxide 1N, potassium chloride,sulphonic acid, dodecanoic acid, nonylphenol, terpene-1 and water, forcleaning crude formations and facilities, for dissolving waxes,asphaltene and other component precipitates in the crude, for enhancingthe physico-chemical properties of the crude such as viscosity, density,API gravity, water/crude emulsion content, reduction of acidity andstimulation of crude production.
 7. The process of using the compound ofbiodegradable surfactants of claim 6 for treating different kinds ofcrude oil, bitumen, greases, oily sands and crude oil spills.